Local Bond-Stretch Coordinates for Anharmonic Vibrational Computations

IF 2.7 2区化学 Q3 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry A Pub Date : 2025-04-02 DOI:10.1021/acs.jpca.4c0770410.1021/acs.jpca.4c07704

Sebastian Riis Thomsen*, Nicolai Machholdt Høyer*, Mads Greisen Højlund* and Ove Christiansen*,

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Abstract

The local bond-stretch (LBS) method is presented as a means of obtaining a set of localized, rectilinear vibrational modes. Three variants of the LBS method are considered: pure LBS, projected LBS (pLBS), and orthogonal, projected LBS (opLBS). These variants feature different degrees of localization and different coupling terms in the kinetic energy operator, such that the most localized method (LBS) has the largest number and magnitude of coupling terms, and the least localized (opLBS) has the least coupling terms. The different LBS variants are exemplified in computations on overtone vibrational spectra of water, nitroxyl (chemical formula HNO), formaldehyde, and 1,3-butadiene computed with a vibrational coupled cluster band Lanczos approach. These spectra are calculated using potential energy surfaces (PESs) obtained with the adaptive density-guided approach (ADGA). We observe faster convergence with respect to the coupling level in the PES when using the LBS variants compared to normal coordinates. Among the LBS variants, pLBS and opLBS appear most promising.

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非调和振动计算的局部键-伸缩坐标

局部键拉伸（LBS）方法是一种获得一组局域直线振动模态的方法。考虑了三种LBS方法：纯LBS，投影LBS （pLBS）和正交投影LBS （opLBS）。这些变体在动能算符中具有不同程度的局部化和不同的耦合项，因此最局部化方法（LBS）的耦合项数量和大小最大，而最小局部化方法（opLBS）的耦合项最少。用振动耦合簇带Lanczos方法计算了水、硝基（化学式HNO）、甲醛和1,3-丁二烯的泛音振动谱，并举例说明了不同的LBS变体。利用自适应密度引导法（ADGA）获得的势能面（PESs）计算这些光谱。我们观察到，与正坐标相比，当使用LBS变量时，相对于PES中的耦合水平，更快的收敛。在LBS变体中，pLBS和opLBS看起来最有前途。

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来源期刊

The Journal of Physical Chemistry A 化学-物理：原子、分子和化学物理

CiteScore

5.20

自引率

10.30%

发文量

922

审稿时长

1.3 months

期刊介绍： The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.